Substituted methyl isopropyl oxocyclohexane derivatives, organoleptic uses thereof and process for preparing same

ABSTRACT

The compounds having the genus defined according to the structure: ##STR1## are useful in augmenting or enhancing the aroma or taste of consumable materials including perfume compositions, colognes and perfumed articles (e.g., solid or liquid anionic, cationic, nonionic or zwitterionic detergents, cosmetic powder compositions, fabric softener compositions and fabric softener articles).

This is a divisional of application Ser. No. 343,571, filed Apr. 26,1982, now U.S. Pat. No. 4,451,403.

BACKGROUND OF THE INVENTION

The instant invention provides substituted methyl isopropyloxocyclohexane derivatives which are novel, defined according to thestructure: ##STR2## wherein the moiety represents one of the structures:##STR3## wherein when the moiety X has the structure: ##STR4## then oneof the lines:

    [++++]

is a carbon-carbon double bond and the other of the lines:

    [++++]

is a carbon-carbon single bond and when the moiety X has the structure:##STR5## then both of the lines:

    [++++]

represent carbon-carbon single bonds;

wherein, one of R₁, R₂ and R₃ represent 2-methyl-1-propenyl or2-methyl-1-propylidenyl; and the other of R₁, R₂ and R₃ representhydrogen; with the provisos that:

(i) when the line:

    [++++]

at the 3-4 position is a double bond, then R₃ is hydrogen or2-methyl-1-propenyl; and

(ii) when the line:

    [++++]

at the 2-3 position is a double bond, then R₂ is hydrogen or2-methyl-1-propenyl.

and uses of said substituted methyl isopropyl oxocyclohexane derivativesfor their organoleptic properties in augmenting or enhancing the aromaof perfume compositions, perfumed articles or colognes.

Chemical compounds which can provide herbaceous, woody, earthy,camphoraceous, tabac-resin-like, guiacwood-like, cardamon, jute-like,spicy, honey, sweaty, ionone-like, smokey, rosey, vetiver-like, fruityand musky aroma nuances are highly desirable in the art of perfumery.Many of the natural materials which provides such fragrances andcontribute such desired nuances to perfumery compositions are high incost, unobtainable at times, vary in quality from one batch to anotherand/or are generally subject to the usual variations of naturalproducts.

There is, accordingly, a continuing effort to find synthetic materialswhich will replace, enhance, or augment the essential fragrances notesprovided by natural essential oils or compositions thereof.

The fundamental problem in creating artificial fragrance agents is thatthe artificial fragrance to be achieved to be as natural as possible.This generally proves to be a difficult task since the mechanism for afragrance development in many fragrance materials is not completelyknown. This is noticeable in products in the fragrance area havingherbaceous, woody, earthy, camphoraceous, tobacco resin-like,guiacwood-like, cardamon, jute-like, spicy, honey, sweaty, ionone-like,smokey, rosey, vetiver-like, fruity and musky aroma nuances.

The substituted methyl isopropyl oxocyclohexane derivatives of myinvention are not known in the prior art. Although substituted alkylisopropyl cyclohexanones are known in the prior art, the disclosure ofsuch compounds does not include the utilization thereof in perfumeryand, furthermore, does not include processes for producing thesubstituted alkyl isopropyl cyclohexanones of my invention. Wiemann, etal and Riand and Brun in the references:

(i) Wiemann, et al, Ann. Chim., 1972, Volume 7, pages 399-499, title:"Contributions a L'Etrude des Mechanismes de Condensations Catalytiquesde Cetones β-Alkyl α-Ethyleniques en Milieu Heterogene et en PhaseVapeur. Etudes Spectrographiques IR, UV, RMN".

(ii) Riand and Brun, Bulletin de la Societe Chimique de France, 1976,Nos. 3-4 (combined) pages 557-562 inclusive, title: "No.105--Spectrometrie de Masse. II--Fragmentations Induites par ImpactElectronique de Cyclohexenones".

disclose the compounds having the structures: ##STR6## produced bydimerization of the compound having the structure: ##STR7## overmagnesium oxide dimerization catalyst in the gas phase according to thereaction: ##STR8##

The prior art process of Riand and Brun or Wiemann, et al does notutilize a liquid phase dimerization and does not utilize the catalystsystems of my invention nor does it carry out a reduction of theresultant cyclohexenone. Furthermore, the reaction mixture produced byRiand and Brun or Wiemann does not give rise to the same mixture ofcompounds which is the starting material for my invention.

Unsaturated cyclic ketones with unsaturated alkylene and alkylidene sidechains are known in the field of perfumery; and unsaturated cyclicalkanols and alkanol acetates with unsaturated alkylene and alkylideneside chains are also known in the art of perfumery but these compoundsare different in kind in structure from the structures of the compoundsof the present invention.

Thus, laevo-carvyl acetate having the structure: ##STR9## is disclosedby Arctander, "Perfume and Flavor Chemicals (Aroma Chemicals)" atMonograph No. 582 to have a refreshing, green-minty, spearmint-likeodor, more "cool" than carvone, not as penetrating but with a peculiar"metallic" undertone . . . sweet, spicy-minty, green and refreshingtaste not as powerful as carvone but overall more pleasant, versatile incharacter". Arctander further states at Monograph No. 578 thatlaevo-carveol having the structure: ##STR10## has an odor which is "morecaraway-like than spearmint-like (according to the majority ofopinions)". Arctander further states that Monograph No. 2770 thatiso-pulegone having the structure: ##STR11## has a "powerful minty,woody, mildly green odor . . . very diffusive and penetrating, not assweet as pulegone, not as tenacious".

Nothing in the prior art discloses the novel and useful and unexpectedlyadvantageous organoleptic utilities of the compounds of my invention andnothing in the prior art discloses or renders obvious the novelcompounds of my invention or the novel products-by-process of myinvention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is the GLC profile for the reaction product of Example A whereinthe mixture defined according to the structure: ##STR12## is producedwherein in the mixture in each of the molecules one of the dashed linesis a carbon-carbon double bond and the other of the dashed lines is acarbon-carbon single bond and the molecules are different.

FIG. 2 is the NMR spectrum for the reaction product of Example Acontaining a mixture of compounds defined according to the structure:##STR13## wherein in the mixture in each of the molecules one of thedashed lines is a carbon-carbon double bond and the other of the dashedlines is a carbon-carbon single bond and the components of the mixtureare different.

FIG. 3 is the infra-red spectrum for the reaction product of Example Acontaining the compounds defined according to the structure: ##STR14##wherein in the mixture in each of molecules, one of the dashed lines isa carbon-carbon double bond and the other of the dashed lines is acarbon-carbon single bond and the compounds are different.

FIG. 4 is the GLC profile for the crude reaction product producedaccording to Example I containing a mixture of compounds definedaccording to the structures: ##STR15## as well as the mixture ofcompounds which is the starting material for producing said compoundsdefined according to the structure: ##STR16##

FIG. 5 is the GLC profile for the bulked distillation fractions 11-19 ofthe distillation product of the reaction product of Example I containingthe compounds having the structures: ##STR17##

FIG. 6 is the NMR spectrum for Peak 1 (indicated by the referencenumeral "2" on the GLC profile of FIG. 4, supra). The compound of Peak 1has the structure: ##STR18##

FIG. 7 is the infra-red spectrum for the compound of Peak 1 of the GLCprofile of FIG. 4 having the structure: ##STR19##

FIG. 8 is the NMR spectrum for Peak 2 of the GLC profile of FIG. 4 whichis indicated by reference numeral "3" on said FIG. 4. Peak 2 signifiesthe compound having the structure: ##STR20##

FIG. 9 is the infra-red spectrum for Peak 2 of the GLC profile of FIG.4, containing the compound having the structure: ##STR21##

FIG. 10 is the NMR spectrum for Peak 3 of the GLC profile of FIG. 4,with Peak 3 being signified by the reference numeral "4". Peak 3contains the compound having the structure: ##STR22##

FIG. 11 is the infra-red spectrum for Peak 3 of the GLC profile of FIG.4 which signifies the compound having the structure: ##STR23##

FIG. 12 is the NMR spectrum for Peak 4A of the GLC profile of FIG. 4which signifies the compound having the structure: ##STR24## Peak 4A isindicated on FIG. 4 by reference numeral "5".

FIG. 13 is the infra-red spectrum for Peak 4A of the GLC profile of FIG.4 signifying the compound having the structure: ##STR25##

FIG. 14 is the NMR spectrum for Peak 4B of the GLC profile of FIG. 4signifying the compound having the structure: ##STR26## or the compoundhaving the structure: ##STR27## Peak 4B is indicated on FIG. 4 to havethe reference numeral "5".

FIG. 15 is the infra-red spectrum for Peak 4B of the GLC profile of FIG.4 which signifies one of the compounds having the structures: ##STR28##Peak 4B is shown by reference numeral "5" on FIG. 4.

FIG. 16 is the NMR spectrum for Peak 5 of the GLC profile of FIG. 4signifying the compounds having the structures: ##STR29## Peak 5 isindicated by the reference numeral "6" on FIG. 4.

FIG. 17 is the infra-red spectrum for Peak 5 of the GLC profile of FIG.4 signifying the compounds having the structures: ##STR30## Peak 5 isindicated on FIG. 4 by reference numeral "6".

FIG. 18 is the GLC profile for bulked fractions 11-19 of Example Iindicating groups of trapped peaks for organoleptic evaluations thusly:

(i) Group "A" is the combination of Peaks 1, 2 and 3;

(ii) Group "B" is Peak 4;

(iii) Group "C" is Peak 5.

FIG. 19 is the GLC profile for the reaction product of Example II whichcontains a mixture of compounds defined according to the structure:##STR31## wherein one of the dashed lines represents a carbon-carbondouble bond and the other of the dashed lines represents a carbon-carbonsingle bond; wherein one of R₁, R₂ and R₃ represents a2-methyl-1-propenyl or 2-methyl-1-propylidenyl; and the other of R₁, R₂and R₃ is hydrogen; with the provisos that:

(i) when the dashed line at the 3-4 position is a double bond, then R₃is hydrogen or 2-methyl-1-propenyl; and

(ii) when the dashed line at the 2-3 position is a double bond, then R₂is hydrogen methyl or 2-methyl-1-propenyl.

FIG. 20 is the NMR spectrum for the major peak of the GLC profile ofFIG. 19 and this major peak has the structure: ##STR32##

FIG. 21 is the infra-red spectrum for the major peak of the GLC profileof FIG. 19 and this major peak has the structure: ##STR33##

FIG. 22 is the GLC profile for the reaction product of Example IIIcontaining a mixture of compounds defined according to the structure:##STR34## wherein one of R₁, R₂ and R₃ represents 2-methyl-1-propenyl or2-methyl-1-propylidenyl; and the other of R₁, R₂ and R₃ is hydrogen.

FIG. 23 is the NMR spectrum for the major peak of the GLC profile ofFIG. 22 and the major peak has the structure: ##STR35##

FIG. 24 is the infra-red spectrum for the major peak of the GLC profileof FIG. 22 and the major peak represents the compound having thestructure: ##STR36##

FIG. 25 is the GLC profile for the reaction product of Example IVcontaining a mixture of compounds defined according to the structure:##STR37## wherein one of the dashed lines represents a carbon-carbondouble bond and the other of the dashed lines represents a carbon-carbonsingle bond; wherein one of R₁, R₂ and R₃ represents 2-methyl-1-propenylor 2-methyl-1-propylidenyl; and the other of R₁, R₂ and R₃ representhydrogen; with the provisos that:

(i) when the dashed line at the 3-4 position is a double bond, then R₃is hydrogen or 2-methyl-1-propenyl; and

(ii) when the dashed line at the 2-3 position is a double bond, then R₂is hydrogen methyl or 2-methyl-1-propenyl.

FIG. 26 is the NMR spectrum for the major peak of the GLC profile ofFIG. 25 and the major peak is for the compound having the structure:##STR38##

FIG. 27 is the infra-red spectrum for the major peak of the GLC profileof FIG. 25 and is for the compound having the structure: ##STR39##

DETAILED DESCRIPTION OF THE DRAWINGS

FIG. 4 is the GLC profile for the crude reaction product producedaccording to Example I.

The conditions are Carbowax column operated at 200° C., isothermal.

The Peak indicated by the reference numeral "1" is the starting materialwhich is a mixture of compounds defined according to the structure:##STR40## wherein in the mixture in each of the molecules one of thedashed lines is a carbon-carbon double bond and the other of the dashedlines is a carbon-carbon single bond and the molecules are different.

The Peaks indicated by reference numerals "2", "3", "4", "5" and "6"represent products produced by means of the dimerization of the compounddefined according to the structure: ##STR41## Thus, the Peak indicatedby reference numeral "2" is "Peak 1" which is the compound having thestructure: ##STR42##

The Peak indicated according to reference numeral "3" is "Peak 2" havingthe structure: ##STR43##

"Peak 3" indicated by reference numeral "4" has the structure: ##STR44##

The Peak signified by reference numeral "5" is a combination of Peaks 4Aand 4B. Peak 4A is the compound having the structure: ##STR45## Peak 4Bis either the compound having the structure: Peak 4B is either thecompound having the structure: ##STR46## and/or the compound having thestructure: ##STR47##

The Peak indicated by reference numeral "6" is Peak 5 which is thecompound having the structure: ##STR48## and/or the compound having thestructure: ##STR49##

FIG. 5 is the GLC profile for bulked distillation fractions 11-19 of thedistillation product of the reaction product of Example I.

The Peak indicated by reference numeral "7" is Peak 1 which is thecompound having the structure: ##STR50##

The Peak indicated by reference numeral "8" is Peak 2 having thestructure: ##STR51##

The Peak indicated by reference numeral "9" is Peak 3 having thestructure: ##STR52##

The Peak indicated by reference numeral "10" is Peak 4A having thestructure: ##STR53##

The Peak indicated by reference numeral "11" is Peak 4B having thestructure: ##STR54##

The peak indicated by reference numeral "12" is Peak 5 having thestructure: ##STR55##

FIG. 18 is the GLC profile for bulked fractions 11-19 of thedistillation product of the reaction product of Example I wherein thePeaks are grouped into three groupings:

Group "A" which is Peaks 1, 2 and 3 indicated by reference numerals"13", "14" and "15"

Group "B" which is Peak 4 indicated by reference numeral "17" and

Group "C" which is Peak 5 indicated by reference numeral "19".

In Group "A", the peak indicated by reference numeral "13" is Peak 1having the structure: ##STR56##

Peak 2 is indicated by reference numeral "14" and has the structure:##STR57##

Peak 3 is indicated by reference numeral "15" and has the structure:##STR58##

Peak 4 is indicated by reference numerals "17" and "18" and have thestructures: ##STR59##

Peak 5 is indicated by reference numeral "19" and has the structure:##STR60##

THE INVENTION

It has now been determined that certain substituted methyl isopropyloxocyclohexane derivatives defined according to the generic structure:##STR61## wherein at least one of the lines:

    [++++]

is a carbon-carbon single bond and the other of the lines:

    [++++]

is either a carbon-carbon single bond or a carbon-carbon double bond;wherein the moiety X represents one of the structures: ##STR62## whereinwhen the moiety X has the structure: ##STR63## then one of the lines:

    [++++]

is a carbon-carbon double bond and the other of the lines:

    [++++]

is a carbon-carbon single bond and when the moiety X has the structure:##STR64## then both of the lines:

    [++++]

represent carbon-carbon single bonds;

wherein one of R₁, R₂ and R₃ represents 2-methyl-1-propenyl or2-methyl-1-propylidenyl; and the other of R₁, R₂ and R₃ representhydrogen; with the provisos that:

(i) when the line [++++] at the 3-4 position is a double bond, then R₃is hydrogen or 2-methyl-1-propenyl; and

(ii) when the line [++++] at the 2-3 position is a double bond, then R₂is hydrogen or 2-methyl-1-propenyl.

are capable of imparting a variety of fragrances to perfumecompositions, colognes and/or perfumed articles.

Briefly, my invention contemplates augmenting or enhancing thefragrances of such consumable materials as perfumes, colognes andperfumed articles by adding thereto a small but effective amount of atleast one of the compounds defined according to the structure: ##STR65##wherein X, R₁, R₂, R₃ and the lines [++++] are defined, supra.

Also contemplated within the scope of my invention are processes forpreparing such compounds and the products produced by such processes.These processes involve the dimerization of a mixture of compoundsdefined according to the structure: ##STR66## wherein in the mixture oneof the dashed lines represents a carbon-carbon double bond and the otherof the dashed lines represents a carbon-carbon single bond using acatalyst which is either an alkali metal hydroxide, an alkaline earthmetal hydroxide, aluminum chloride, sulfuric acid, or pyrrolidiniumacetate in the presence of an inert solvent such as ethanol, methanol,isopropanol, n-propanol, n-hexane, or toluene. The process can becarried out by producing the compound defined according to thestructure: ##STR67## by carrying out the "aldol condensation" ofisobutyraldehyde having the structure: ##STR68## with acetone using thesame solvent system as defined above and the same catalyst system asdefined above.

The reaction of the isobutyraldehyde with the acetone followed by thedimerization of the resulting compound is shown as follows: ##STR69##wherein one of the dashed lines represents a carbon-carbon double bondand the other of the dashed lines represents a carbon-carbon single bondand wherein one of R₁, R₂ and R₃ represents 2-methyl-1-propenyl or2-methyl-1-propylidenyl, and the other of R₁, R₂ and R₃ representhydrogen; with the provisos that:

(i) when the dashed line at the 3-4 position is a double bond, when R₃is hydrogen or 2-methyl-1-propenyl; and

(ii) when the dashed line at the 2-3 position is a double bond, then R₂is hydrogen or 2-methyl-1 propenyl.

The dimerization reaction is carried out at a temperature in the rangeof from about 25° C. up to about 120° C. at atmospheric pressure in thepresence of:

(a) a solvent which can be a hydrocarbon such as n-hexane or toluene; aninsert alkanol such as methyl ethanol or isopropyl alcohol; and

(b) a catalyst which is either acidic or basic such as an alkali metalhydroxide such as potassium hydroxide or sodium hydroxide; an alkalineearth metal hydroxide such as barium hydroxide; aluminum chloride; or anamphoteric catalyst such as pyrrolidinium acetate defined according tothe structure: ##STR70##

As will be seen by an examination of the GLC profiles in the figures assummarized, supra, the isomer ratios of the reaction product mixturedefined according to the structure: ##STR71## will vary and depend uponthe following reaction variables: (a) temperature of reaction;

(b) time or reaction;

(c) nature of catalyst;

(d) concentration of catalyst;

(e) nature of solvent;

(f) concentration of reactant in solvent;

(g) ratio of catalyst to reactant.

When carrying out the reaction between the isobutyraldehyde and acetonein situ, the mole ratio of isobutyraldehyde:acetone may vary from1.5:0.5 up to 0.5:1.5 isobutyraldehyde:acetone. The reaction temperaturerange may vary from about 25° C. up to about 120° C. and is preferablythe temperature at which the reaction mass will reflux at atmosphericpressure. Thus, when carrying out the reaction using a methyl alcoholcatalyst wherein the reactant concentration is 4 kg. per liter usingmethanol, the reaction temperature is maintained at 50°-52° C.

The concentration of catalyst in the reaction mass may vary from about50 grams per liter up to about 400 grams per liter. The nature of thesolvent may vary as set forth above with the preferred solvents beingmethanol, ethanol and isopropyl alcohol. The nature of the catalyst mayvary as set forth above with the preferred catalysts being sodiumhydroxide, potassium hydroxide and barium hydroxide.

If desired the substituted methyl isopropyl cyclohexenones definedaccording to the generic structure: ##STR72## may be separated andobtained in pure form or in substantially pure form by conventionalpurification techniques. Thus, the products can be purified and/orisolated by distillation, extraction, crystallization, preparativechromatographic techniques (column chromatography and vapor phasechromatography) and the like. It has been found desirable to purify thesubstituted methyl isopropyl cyclohexenone derivatives having thestructure: ##STR73## of my invention by fractional fractionaldistillation in vacuo, prior to carrying out the reduction reactions toform the compounds defined according to the structure: ##STR74## morespecifically the compounds having the structures: ##STR75## wherein thedashed lines, X, R₁, R₂ and R₃ are defined, supra and the lines [++++]are also defined supra.

The reduction reaction for the reduction of the compounds definedaccording to the generic structure: ##STR76## to form the compoundsdefined according to the generic structure: ##STR77## can be carried outusing either an alkali metal borohydride such as sodium borohydride,potassium borohydride or lithium borohydride or can be carried out usinghydrogen and a catalyst such as palladium on carbon (3%, 5%, 7% or 10%palladium on carbon); palladium on calcium carbonate (3%, 5%, or 10%palladium on calcium carbonate) or palladium on barium sulfate (5% or10% palladium on barium sulfate).

When carrying the reaction using the alkali metal borohydride, thecompounds formed will be the cyclohexenol derivatives defined accordingto the structure: ##STR78## according to the reaction: ##STR79## whereinthe dashed lines and R₁, R₂ and R₃ are defined, supra. The reaction iscarried out in the presence of a solvent which is inert to the reactionmass such as methanol, ethanol, isopropyl alcohol or n-propanol. Thealkali metal borohydride usable is sodium borohydride, potassiumborohydride or lithium borohydride with sodium borohydride beingpreferred because of its availability and low cost. The concentration ofalkali metal borohydride in the reaction mass may vary from about 20grams per liter of reaction mass up to about 50 grams per liter ofreaction mass. The concentration of ketone mixture or ketone productdefined according to the structure: ##STR80## may vary from 200 gramsper liter up to about 800 grams per liter with a preferred concentrationof ketone being about 550-650 grams per liter. The reaction temperatureis in the range of 40°-70° C. with a preferred reaction temperature of45°-55° C. at atmospheric pressure. Utilization of pressures greaterthan atmospheric will permit an increase in reaction temperature and ashorter reaction times but no advantage in yield or conversion existsusing such higher pressures.

In carrying out the reduction of the ketones having the structure:##STR81## to form the cyclohexanone derivative defined according to thestructure: ##STR82## hydrogen is used as the reducing agent using acatalyst such as palladium, palladium on a carbon support, palladium ona calcium carbonate support or palladium on a barium sulfate support.The most preferred catalyst is 5% palladium on carbon. The hydrogenpressure may vary from 50 psig up to 10 atmospheres with a preferredhydrogen pressure of 100 psig. The mole ratio of hydrogen:ketonereactant defined according to the structure: ##STR83## is in the rangeof from 1:1 hydrogen:ketone up to about 3:1 hydrogen:ketone with apreferred mole ratio of 1:1 hydrogen:ketone reactant. The reaction iscarried out in an inert solvent such as isopropyl alcohol, n-propylalcohol, methanol or ethanol. The temperature of reaction according tothe reaction scheme: ##STR84## may vary from about 20° C. up to about100° C. Higher temperatures of reaction do not give rise to higheryields but instead give rise to an increased concentration of undesiredby-product which are difficult to separate from the reaction productdefined according to the structure: ##STR85##

The formation of the compound or mixture of compounds of my inventiondefined according to the structure: ##STR86## wherein R₁, R₂, R₃ and thedashed lines are defined, supra is carried out according to thereaction: ##STR87## wherein acetic anhydride is reacted with thecyclohexenol derivative(s) produced as set forth, supra. Thecyclohexenol are first separated from the reaction mass as by fractionaldistillation in vacuo and then reacted with the acetic anhydride.

The reaction temperature is preferably in the range of from about 90° C.up to about 120° C. and is preferably at 100° C. The mole ratio ofacetic anhydride:alcohol reactant may vary from about 1:0.5 up to about2:1 alcohol:acetic anhydride. The time of reaction may vary from aboutone hour up to about three hours depending upon the temperature ofreaction. Higher pressures of reaction (greater than atmospheric) giverise to lower temperatures of reaction and consequently shorter times ofreaction. However it is most preferred and convenient to carry out thereaction at a 100° C. and one atmosphere pressure. At the end of thereaction the reaction mass is washed and neutralized with a weak basesuch as sodium carbonate. Subsequently the reaction mass is washed withwater, dried and distilled on a fractional distillation in vacuo toyield the desired acetate which then has uses in perfumery, colognes andperfumed articles as set forth, infra.

In each of the foregoing cases the reaction product after the reactionmay be "worked up" whereby various groups of reaction products orindividual reaction products may be obtained in pure form or inadmixture by conventional purification techniques. Thus, the productscan be purified, isolated or formed into desired mixtures by means offractional distillation, extraction, crystallization, preparativechromatographic techniques (column chromatography and vapor phasechromatography) and the like. It has been found most desirable to purifythe substituted methyl isopropyl oxocyclohexane derivatives of myinvention by fractional distillation in vacuo.

Examples of the compounds produced according to the processes of myinvention and the organoleptic properties thereof are as follows:

                  TABLE I                                                         ______________________________________                                        Structure Defining                                                                            Perfume                                                       Mixture Produced                                                                              Properties                                                    ______________________________________                                         ##STR88##      A herbaceous, woody, earthy, camphoraceous tobacco                            resin-like guiacwood-like, cardamom-like, jute-like,                          spicy, honey and sweaty aroma profile.                        produced according to                                                         Example III, infra.                                                            ##STR89##      A woody, fruity ionone-like, smokey, rosey, vetiver-like,                     amphoraceous, fruity and musky aroma profile.                 produced according to                                                         Example II.                                                                     Mixture of compounds                                                                        A woody, ionone-like                                          defined according to                                                                          aroma profile.                                                the structure:                                                                 ##STR90##                                                                      produced according to                                                       Example IV, infra.                                                            ______________________________________                                    

The substituted methyl isopropyl oxocyclohexane derivatives of myinvention can be used alone or in combination to contribute herbaceous,woody, earthy, camphoraceous, tobacco resin-like, guiacwood, cardamom,jute-like, spicy, honey, sweaty, ionone-like, smokey, rosey,vetiver-like, fruity and musky aroma nuances to perfumes, perfumedarticles and colognes.

As olfactory agents the substituted methyl isopropyl oxocyclohexanederivatives of my invention can be formulated into or used as componentsof a "perfume composition" or can be used as components of a "perfumedarticle" or the perfume composition may be added to "perfumed articles".

The term "perfume composition" is used herein to meet a mixture oforganic compounds including for example alcohols (other than thealcohols of my invention), aldehydes, ketones (other than the ketones ofmy invention), nitriles, ethers, lactones, natural essential oils,synthetic essential oils and frequently hydro carbons which are admixedso that the combined odors of the individual components produce apleasant or desired fragrance. Such perfume compositions usuallycontain: (a) the main note or the "bouquet" or foundation stone of thecomposition; (b) modifiers which round off and accompany the main note;(c) fixatives which include odorous substances which lend a particularnote to the perfume throughout all stages of evaporation and substanceswhich retard evaporation; and (d) topnotes which are usuallylow-boiling, fresh-smelling materials.

In perfume compositions, the individual component will contribute itsparticular olfactory characteristics, but the overall effect of theperfume composition will be the sum total of the effects of each of theingredients and possibly even more than the sum total of each of theeffects of each of the ingredients if there exists synergism amongst theingredients. Thus, the individual compounds of this invention ormixtures thereof can be used to alter, augment or enhance the aromacharacteristics of a perfume composition, for example, by highlightingor moderating the olfactory reaction contributed by another ingredientin the composition.

The amount of the substituted methyl isopropyl oxocyclohexanederivatives of this invention which will be effective in perfumecompositions depends on many factors, including the other ingredients,their amounts and the effects which are desired. It has been found thatperfume compositions containing as little as 0.05% of the substitutedmethyl isopropyl oxocyclohexane derivatives of this invention, or evenless, can be used to impart an interesting herbaceous, woody, earthy,camphoraceous, tobacco resin-like, guiacwood-like, cardamom-like,jute-like, spicy, honey, sweaty, ionone-like, smokey, rosey,vetiver-like, fruity and musky aroma nuances to soaps, liquid and solidcationic, anionic, nonionic and zwitterionic detergents, cosmeticpowders, liquid and solid fabric softeners, fabric softeners articles,optical brightener compositions and other products. The amount employedcan range up to 50% or higher and will depend on considerations of cost,nature of the end product and the effect desired on the finished productand the particular fragrance sought.

The substituted methyl isopropyl oxocyclohexane derivatives of thisinvention can be used alone or in a perfume composition as an olfactorycomponent in detergents and soaps, space odorants and deodorants;perfumes; colognes, toilet waters; bath salts; hair preparations such aslacquers, brilliantines, pomades and shampoos; cosmetic preparationssuch as creams, deodorants, hand lotions and sun screens; powders suchas talcs, dusting powders, face powders and the like. When used as anolfactory component of a perfumed article, as little as 0.01% of one ormore of the substituted methyl isopropyl oxocyclohexane derivatives ofmy invention will suffice to impart an interesting herbaceous, woody,earthy, camphoraceous, tobacco resin-like, guiacwood, cardamom,jute-like, spicy, honey, sweaty, ionone-like, smokey, rosey,vetiver-like, fruity and musky aroma nuances. Generally, no more than0.5% (by weight of the perfumed article) is required. Thus, the range ofuse of the substituted methyl isopropyl oxocyclohexane derivatives of myinvention in perfumed articles is 0.01% up to 0.5% and the use inperfume compositions per se is from 0.05% up to 50% of the substitutedmethyl isopropyl oxocyclohexane derivatives of my invention.

In addition, the perfume compositions can contain a vehicle or carrierfor the substituted methyl isopropyl oxocyclohexane derivatives of myinvention taken alone or taken together with other ingredients. Thevehicle can be a liquid such as an alcohol such as ethanol, a glycolsuch as propylene glycol or the like. The carrier can be an absorbentsolid such as a gum (e.g., gum arabic or guar gum or xanthan gum) orcomponents for encapsulating the composition such as gelatin (as bycoacervation) which can be used to form a capsule wall surrounding theperfume oil, or a urea formaldehyde resin which is formed bypolymerization to form a capsule wall surrounding the perfume oil.

It will thus be apparent that the substituted methyl isopropyloxocyclohexane derivatives of my invention can be used to alter, modify,augment or enhance sensory properties, particularly organolepticproperties such as fragrances of a wide variety of consumable materials.

The following Examples A and I serves to illustrate methods forproducing precursors which are used in producing the products of myinvention. The following Examples II-IV inclusive, serve to illustratethe processes for carrying out the chemical syntheses of the products ofmy invention. The following Examples V et seq. set forth the uses of theproducts of Examples II-IV of my invention. The invention is to beconsidered restricted to these examples only as indicated in theappended claims.

All parts and percentages given herein are by weight unless otherwisespecified.

EXAMPLE A PREPARATION OF 5-METHYL-HEXENE-2-ONE MIXTURE

Reaction: ##STR91##

Into a 5 liter reaction flask equipped with stirrer, thermometer,condenser, addition funnel and heating mantle and fitted with a Soxhletapparatus containing a thimble filled with barium hydroxide (200 grams)is placed a mixture of 1.5 kg of isobutyraldehyde and 1.4 kg of acetone.

The reaction mass is refluxed and the resultant 5-methyl-hexene-2-onemixture is collected in the reaction flask for a period of 4 hours.

At the end of the 4 hour period, the reaction mass is stripped of excessreactants and 2.3 kg of 5-methyl-hexene-2-one compounds are collectedvia distillation at a temperature of 74° C. and a pressure of 0.8 mm/Hgpressure.

FIG. 1 is the GLC profile of the reaction product (conditions: Carbowaxcolumn operated at 200° C. isothermal).

FIG. 2 is the NMR spectrum for the reaction product collected viadistillation at the temperature of 74° C. and 0.8 mm/Hg pressure.

FIG. 3 is the infra-red spectrum for the resulting product which is amixture of compounds defined according to the structure: ##STR92##wherein in the mixture, in each of the molecules, one of the dashedlines is a carbon-carbon double bond and the other of the dashed linesis a carbon-carbon single bond and the molecules of the mixture aredifferent.

EXAMPLE I DIMERIZATION OF 5-METHYL-HEXENE-2-ONE MIXTURE

Reaction: ##STR93## wherein one of R₁, R₂ or R₃ is 2-methyl-1-propenylhaving the structure: ##STR94## or 2-methyl-1-propylidenyl having thestructure: ##STR95## and the other two of R₁, R₂ or R₃ is hydrogen; andwherein in the mixture, in each of the molecules of the mixture, one ofthe dashed lines is a carbon-carbon double bond and the other of thedashed lines is a carbon-carbon single bond and wherein the molecules ofthe mixture are represented thusly: ##STR96##

Into a 5 liter reaction flask equipped with stirrer, thermometer,condenser, addition funnel, heating mantle, cooling bath andTherm-o-watch apparatus is placed 100 grams of potassium hydroxide. 500ml of methanol is placed in an addition funnel. Over a period of 10minutes, the methanol is added to the KOH. After the methanol is mixedwith the KOH, the resulting mixture is heated to 50° C. and over aperiod of 1 hour, the 5-methyl-hexene-2-one mixture (2 kg) producedaccording to Example A (boiling point 74° C. at 0.8 mm/Hg pressure) isadded to the reaction mass while maintaining the reaction mass at50°-55° C. At the end of the addition, the reaction mass is stirred fora period of 1.5 hours at 50°-51° C. The reaction mass is then added totwo liters of water and the resulting organic layer is washed with twoliters of water to a pH of 7. The organic layer is then distilled on a24" Goodloe column to yield 917.2 grams of product and the fractionsresulting from this distillation are as follows:

    ______________________________________                                               Vapor    Liquid                 Weight of                              Fraction                                                                             Temp.    Temp.    Pressure                                                                             Reflux Fraction                               Number (°C.)                                                                           (°C.)                                                                           mm/Hg  Ratio  (grams)                                ______________________________________                                        1      60/85    147/143  0.4/.25                                                                              9:1    47.2                                   2      92       140       0.25  9:1    44.5                                   3      98       140       0.30  9:1    36.3                                   4      84       139       0.22  9:1    44.7                                   5      88       141       0.40  9:1    39.9                                   6      88       142       0.40  9:1    42.0                                   7      88/95    140/141  0.4/0.4                                                                              9:1    41.0                                   8      104      145      0.7    9:1    45.7                                   9      101      148      0.6    9:1    43.1                                   10     103      148      0.5    9:1    39.9                                   11     102      148      0.4    9:1    48.2                                   12     102      148      0.4    9:1    49.8                                   13     103      149      0.4    9:1    41.2                                   14     104      150      0.4    9:1    24.8                                   15     103      150      0.4    9:1    47.0                                   16      92/100  145/147  0.4/0.4                                                                              2:1    36.4                                   17     93       142      0.4    2:1    48.7                                   18     93       143      0.4    2:1    41.6                                   19     93       146      0.4    2:1    45.1                                   20     93       150      0.4    2:1    38.1                                   21     95       195      0.5    2:1    39.6                                   ______________________________________                                    

Fractions 7-22 are bulked for the purposes of organoleptic evaluation.From an aroma standpoint, bulked fractions 7-22 have a peppery,guiacwood-like, vetiver-like, sandalwood-like aroma with a sauge sclareetopnote and a musky undertone.

FIG. 4 is the GLC profile for the crude reaction product (GLCconditions: Carbowax column operated at 200° C. isothermal).

The Peak on the GLC profile indicated by the reference numeral "1"represents the starting material having the structure: ##STR97## amixture, wherein in the mixture in one of the molecules one of thedashed lines is a carbon-carbon double bond and the other of the dashedlines is a carbon-carbon single bond and in the other of the molecules,the other of the dashed lines is a carbon-carbon double bond.

The Peak indicated by the reference numeral "2", Peak 1, has thestructure: ##STR98##

The Peak indicated by the reference numeral "3", Peak 2, has thestructure: ##STR99##

The Peak indicated by the reference numeral "4", Peak 3, has thestructure: ##STR100##

The Group of Peaks indicated by the reference numeral "5" is a mixtureof Peaks 4A and 4B. Peak 4A has the structure: ##STR101## Peak 4B hasthe structure: ##STR102##

The Peak indicated by reference numeral "6" is Peak 5 and it has thestructure: ##STR103##

FIG. 5 is the GLC profile for the bulked distillation fractions 11-19 ofthe foregoing distillation of the foregoing reaction product.

The Peak indicated by reference numeral "7" is Peak 1 having thestructure: ##STR104##

The Peak indicated by reference numeral "8" is Peak 2 having thestructure: ##STR105##

The Peak indicated by reference numeral "9" is Peak 3 having thestructure: ##STR106##

The Peak indicated by reference numeral "10" is Peak 4A having thestructure: ##STR107##

The Peak indicated by reference numeral "11" is Peak 4B having thestructure: ##STR108##

The Peak indicated by reference numeral "12" is Peak 5 having thestructure: ##STR109##

FIG. 6 is the NMR spectrum for Peak 1 having the structure: ##STR110##

FIG. 7 is the IR spectrum for Peak 1 of the foregoing GLC profile havingthe structure: ##STR111##

FIG. 8 is the NMR spectrum for Peak 2 of the foregoing GLC profilehaving the structure: ##STR112##

FIG. 9 is the infra-red spectrum for Peak 2 of the foregoing GLC profilehaving the structure: ##STR113##

FIG. 10 is the NMR spectrum for Peak 3 of the foregoing GLC profilehaving the structure: ##STR114##

FIG. 11 is the infra-red spectrum for Peak 3 of the foregoing GLCprofile having the structure: ##STR115##

FIG. 12 is the NMR spectrum for Peak 4A of the foregoing GLC profilehaving the structure: ##STR116##

FIG. 13 is the infra-red spectrum for Peak 4A of the foregoing GLCprofile having the structure: ##STR117##

FIG. 14 is the NMR spectrum for Peak 4B of the foregoing GLC profilehaving the structure: ##STR118##

FIG. 15 is the infra-red spectrum for Peak 4B of the foregoing GLCprofile having the structure: ##STR119##

FIG. 16 is the NMR spectrum for Peak 5 of the foregoing GLC profilehaving the structure: ##STR120##

FIG. 17 is the infra-red spectrum for Peak 5 of the foregoing GLCprofile having the structure: ##STR121##

FIG. 18 is the GLC profile for bulked fractions 11-19.

The Peaks of the GLC profile are grouped as follows:

Group "A" is a mixture of Peaks 1, 2 and 3. Group "A" has a sweaty,burnt grass aroma.

Group "B" is a mixture of Peaks 4A and 4B. Group "B" has an intensepeppery, guiacwood, vetiver, sandalwood-like aroma with a sauge sclareetopnote and a musky undertone.

Group "C" is Peak 5. Group "C" has a green, vetiver aroma.

EXAMPLE II PREPARATION OF REDUCTION OF METHYL ISOPROPYL CYCLOHEXENONEMIXTURE USING ALKALI METAL BOROHYDRIDES

Reaction: ##STR122## (wherein the dashed lines and R₁, R₂ and R₃ aredefined, supra.)

Into a 3 liter reaction flask equipped with stirrer, thermometer, refluxcondenser, dropping funnel, nitrogen blanket apparatus, cooling bath andheating mantle are placed 39 grams of sodium borohydride and 300 ml ofanhydrous isopropyl alcohol. Into the dropping funnel is placed 500grams of the bulked distillation product, fractions 11-19 of the ketonemixture produced according to Example I, supra defined according to thestructure: ##STR123## While the temperature is being raised from 25°-50°C., and over a period of one hour the ketone mixture of bulked fractions11-19 of Example I is added to the sodium borohydride-isopropyl alcoholmixture. At the end of the addition the reaction mass is maintained at45°-50° C. with stirring for a period of three hours.

The reaction mass is then added to 1 liter of 10% hydrochloric acid andthe organic layer is washed with one liter of a 10% sodium chloridesolution.

The reaction mass is then distilled yielding the following fractions:

    ______________________________________                                                Vapor    Liquid             Weight of                                 Fraction                                                                              Temp.    Temp.     Pressure Fraction                                  Number  (°C.)                                                                           (°C.)                                                                            mm/Hg.   (grams)                                   ______________________________________                                        1       85/90    115/118   0.6      11.7                                      2       90       117       0.5      12.2                                      3       85       117       0.5      11.3                                      4       95       118       0.5      18.7                                      5       94       118       0.5      19.6                                      6       94       119       0.5      21.8                                      7       94       120       0.5      23.8                                      8       94       120       0.5      21.4                                      9       91       121       0.5      23.5                                      10      89       121       0.5      21.9                                      11      93       122       0.5      22.7                                      12      94       122       0.5      20.9                                      13      93       124       0.5      19.1                                      14      89       125       0.5      20.7                                      15      89       127       0.5      19.6                                      16      89       129       0.5      19.8                                      17      89       134       0.5      19.4                                      18      89       149       0.5      20.7                                      19      89       165       0.5      10.4                                      20      89       192       0.5      14.2                                      ______________________________________                                    

FIG. 19 is the GLC profile for the foregoing reaction product prior todistillation.

FIG. 20 is the NMR spectrum for the major peak of the GLC profile ofFIG. 19, having the structure: ##STR124##

FIG. 21 is the infra-red spectrum for the major peak of the GLC profileof FIG. 19, for the compound having the structure: ##STR125##

Fractions 1-20 are bulked for further reaction in Example IV and forperfume use in the following examples. Bulked fractions 1-20 have awoody, fruity, ionone-like, smokey, rosey, vetiver-like, camphoraceous,fruity and musky aroma profile.

EXAMPLE III PREPARATION OF REDUCTION OF SUBSTITUTED METHYL ISOPROPYLCYCLOHEXENONE MIXTURE WITH HYDROGEN AND A PALLADIUM ON CARBON CATALYST

Reaction: ##STR126##

Into a 1 liter autoclave is placed 100 grams of bulked distillation offractions 11-19 of Example I defined according to the structure:##STR127## wherein the dashed lines and R₁, R₂ and R₃ are defined,supra. 400 ml of anhydride isopropyl alcohol and 5 grams of 10%palladium on carbon are charged into the autoclave which is a Parrpressure shaker autoclave. The apparatus is purged several times withhydrogen. Reduction is carried out over a period of 1.5 hours at 100psig hydrogen pressure. It is ascertained that the mole ratio ofhydrogen to cyclohexenone reactant mixture is 1:1.

Infra-red, NMR, and mass spectrum analysis confirm that the reactionproduct is a mixture of compounds defined according to the structure:##STR128## wherein R₁, R₂ and R₃ are defined, supra.

The reaction mass is distilled on a 12" goodloe column yielding thefollowing fractions:

    ______________________________________                                        Fraction Vapor    Liquid    Vacuum  Weight of                                 Number   Temp.    Temp.     mm/Hg.  Fractions                                 ______________________________________                                        1        70/75    115/115   0.4/0.4 13.3                                      2        78       115       0.4     14.4                                      3        71       112       0.3     15.6                                      4        72       114       0.3     20.5                                      5        73       115       0.3     20.0                                      6        74       115       0.3     19.7                                      7        74       116       0.3     20.2                                      8        77       119       0.3     27.0                                      9        80       121       0.3     27.1                                      10       80       121       0.3     25.3                                      11       80       121       0.3     24.8                                      12       80       121       0.3     22.5                                      13       80       122       0.3     19.2                                      14       80       125       0.3     16.8                                      15       82       130       0.3     26.5                                      16       86       130       0.3     26.1                                      17       91       131       0.3     26.1                                      18       91       132       0.3     23.1                                      19       93       171       0.3     27.2                                      20       90       220       0.3     10.4                                      ______________________________________                                    

Fractions 1-20 are bulked for subsequent use in perfumery in theperfumery and perfumed article examples, infra.

Fraction 1-20 have a herbaceous, woody, earthy, camphoraceous, tobaccoresin-like, quiacwood-like, cardamom, jute-like, spicy, honey and sweatyaroma profile.

FIG. 22 is the GLC profile of the reaction product prior todistillation.

FIG. 23 is the NMR spectrum for the major peak of the GLC profile ofFIG. 22 for the compound having the structure: ##STR129##

FIG. 24 is the infra-red spectrum for the major peak of the GLC profileof FIG. 22 for the compound having the structure: ##STR130##

EXAMPLE IV PREPARATION OF ACETYLATION OF CYCLOHEXENOL DERIVATIVE MIXTUREPRODUCED ACCORDING TO EXAMPLE II

Reaction: ##STR131## (wherein the dashed lines and R₁, R₂ and R₃ aredefined, supra.)

Into a 2 liter reaction flask equipped with stirrer, thermometer, refluxcondenser, dropping funnel and heating mantle is placed 250 ml aceticanhydride. The acetic anhydride is heated to 110° C. 324 grams of thecyclohexenol reaction product produced according to Example II definedaccording to the structure: ##STR132## (bulked fractions 1-20) is placedin the dropping funnel. While maintaining the reaction mass at 100° C.the cyclohexenol reaction product of Example II (bulked fractions 1-20)is added to the acetic anhydride over a period of three hours. At theend of the reaction the reaction mass is stirred at 100° C. for anadditional ten minutes.

The reaction mass is added to one liter of a 10% sodium chloridesolution and the organic layer is then washed as follows:

(a) one 1 liter portion of 10% sodium carbonate;

(b) one 1 liter portion of water.

The reaction mass is then distilled yielding the following fractions:

    ______________________________________                                        Fraction                                                                              Vapor   Liquid    Vacuum Reflux Wgt. of                               No.     Temp.   Temp.     mm/Hg. Ratio  Fractions                             ______________________________________                                        1       49/41   107/105   3.5/3.5                                                                              9:1/9:1                                                                              6.8                                   2       46      105       0.9    9:1    14.2                                  3       46      105       0.35   9:1    12.4                                  4       47      112       0.35   9:1    13.8                                  5       77      115       0.4    4:1    18.8                                  6       88      127       0.7    4:1    20.7                                  7       94      127       0.7    4:1    20.8                                  8       81      128       0.4    4:1    19.7                                  9       87      129       0.35   4:1    20.4                                  10      86      130       0.4    4:1    20.4                                  11      86      131       0.4    4:1    20.6                                  12      86      131       0.4    4:1    18.6                                  13      86      133       0.4    4:1    18.0                                  14      86      135       0.4    4:1    17.3                                  15      86      140       0.4    4:1    15.5                                  16      88      160       0.4    4:1    14.6                                  17      90      193       0.4    4:1    12.8                                  18      84      245       0.4    4:1    9.0                                   ______________________________________                                    

Fractions 1-18 are bulked and utilized as such in the followingperfumery and perfumed article examples.

Bulked fractions 1-18 have an ionone-like, woody aroma.

FIG. 25 is the GLC profile of the reaction product prior todistillation.

FIG. 26 is the NMR spectrum for the major peak of the GLC profile ofFIG. 25 and is for the compound defined according to the structure:##STR133##

FIG. 27 is the infra-red spectrum for the major peak of the GLC profileof FIG. 25 which is for the compound having the structure: ##STR134##

EXAMPLE V PERFUME FORMULATION

The following sandal cologne perfume formulation is prepared:

    ______________________________________                                        Ingredients              Parts by Weight                                      ______________________________________                                            Bergamot oil                 200                                              Orange oil                   150                                              Lemon oil                    100                                              Mandarin oil                  50                                              Eugenol                       10                                              4-(4-methyl-4-hydroxyamyl                                                     delta.sup.3 -cyclohexene      30                                              carboxaldehyde                                                                3-methyl-4(2,6,6-trimethyl-                                                   2-cyclohexene-1-yl)-          5                                               3-buten-2-one                                                                 methyl-N3,7-dimethyl-                                                         7-hydroxy octylidene          5                                               anthranilate                                                               ##STR135##                5                                                                           2-methyl-5(2-exo-methyl-3-methylene-                                          bicyclo-[2.2.1]-hept-2-yl)3-                                     100          penten-2-ol (prepared according                                               to U.S. Pat. No. 4,000,050)                                                   Mixture of substituted cyclohexenol                                           derivatives prepared                                              40          according to Example II, bulked                                               fractions 1-20                                       ______________________________________                                    

The mixture of substituted cyclohexenol derivatives prepared accordingto Example II in parts to the sandal cologne formulation a woody,fruity, ionone, smokey, rosey, vetiver-like camphoraceous and muskyaroma nuances.

The overall aroma profile of this perfume formulation may be describedas sandalwood-like with woody, fruity, ionone, smokey, rosey, vetiverand camphoraceous undertones and woody, fruity, rosey, camphoraceous andmusky topnotes.

EXAMPLE VI PERFUME FORMULATION

The following sandal cologne perfume formulation is prepared:

    ______________________________________                                        Ingredients              Parts by Weight                                      ______________________________________                                            Bergamot oil                 200                                              Orange oil                   150                                              Lemon oil                    100                                              Mandarin oil                  50                                              Eugenol                       10                                              4-(4-methyl-4-hydroxy amyl                                                    delta.sup.3 -cyclohexene      30                                              carboxaldehyde                                                                3-methyl-4(2,6,6-trimethyl-                                                   2-cyclohexene-1-yl)-          5                                               3-buten-2-one                                                                 methyl-N3,7-dimethyl-                                                         7-hydroxy-octylidene          5                                               anthranilate                                                               ##STR136##                                                                         5                                                                           2-methyl-5(2-exo-methyl-3-methylene-                                          bicyclo-[2.2.1]-hept-2-yl)3-                                                  penten-2-ol (prepared according                                                                            100                                              to U.S. Pat. No. 4,000,050)                                                   Mixture of substituted cyclohexanones                                         prepared according to Example III,                                                                          40                                              bulked fractions 1-20                                                     ______________________________________                                    

The mixture of substituted cyclohexanones (bulked fractions 1-20)produced according to Example III adds to this sandal cologneformulation an excellent herbaceous, woody, earthy, camphoraceous,tobacco resin-like, guiacwood, cardamon, jute-like, sweaty, honey andspicy aroma profile.

In combination, the overall fragrance can be described as sandalwoodwith herbaceous woody, earthy, camphoraceous, tobacco resin-like,guiacwood-like, cardamon and jute-like undertones and sweaty, honey andspicy topnotes.

EXAMPLE VII LILAC PERFUME

The following mixture is prepared:

    ______________________________________                                        Ingredients            Parts by Weight                                        ______________________________________                                            Terpineol                  448                                                Hydroxy citronellal        133                                                Heliotropin                160                                                Phenylethyl alcohol        50                                                 Benzyl acetate             82                                                 Anisaldehyde               95                                                 Oil of cananga             6                                                  Coumarin                   3                                                  Alpha ionone               6                                                  Methyl jasmonate           8                                                  2,3-dimethyl-hydroquinone  6                                                  p-methoxy acetophenone     3                                                  Mixture of acetylated cyclohexenol                                            derivatives prepared according                                                to Example IV (bulked fractions                                                                          35                                                 1-18)                                                                     ______________________________________                                    

The addition of the acetylated cyclohexenol derivative mixture preparedaccording to Example IV (bulked fractions 1-18) adds a woody,ionone-like aroma to this lilac perfume.

In general the lilac perfume can now be described as being lilac withwoody, ionone-like undertones and more "natural-like".

EXAMPLE VIII PREPARATION OF A COSMETIC POWDER COMPOSITION

A cosmetic powder is prepared by mixing in a ball mill 100 grams oftalcum powder with 0.25 grams of the perfume substance set forth inTable II below. The resulting substance has an excellent aroma as setforth in Table II below:

                  TABLE II                                                        ______________________________________                                        Substance         Aroma                                                       ______________________________________                                        Mixture of substituted                                                                          A woody, fruity, ionone,                                    cyclohexanol prepared                                                                           smokey, rosey, vetiver,                                     according to Example II                                                                         camphoraceous, musky                                        (bulked fractions 1-20)                                                                         aroma profile.                                              Mixture of substituted                                                                          A herbaceous, woody,                                        cyclohexenone derivatives                                                                       earthy, camphoraceous,                                      prepared according to                                                                           tobacco resin-like,                                         Example III (bulked                                                                             guiacqood-like, cardamom,                                   fractions 1-20)   jute-like, sweaty, honey                                                      and spicy aroma profile.                                    Acetylated cyclohexenol                                                                         A woody, ionone-like                                        derivative mixture                                                                              aroma.                                                      prepared in accordance                                                        with Example IV (bulked                                                       fractions 1-18)                                                               Perfume composition of                                                                          A sandalwood aroma with                                     Example V         woody, fruity, ionone,                                                        smokey, rosey, vetiver                                                        and camphoraceous under-                                                      tones and woody, fruity,                                                      rosey, camphoraceous                                                          and musky topnotes.                                         Perfume composition of                                                                          A sandalwood aroma with                                     Example VI        herbaceous, woody, earthy,                                                    camphoraceous, tobacco                                                        resin-like, guiacwood,                                                        cardamom and jute-like                                                        undertones and sweaty,                                                        honey and spicy topnotes.                                   Perfume composition of                                                                          A lilac aroma with ionone-                                  Example VII       like and woody undertones.                                  ______________________________________                                    

EXAMPLE IX PERFUMED LIQUID DETERGENT

Concentrated liquid detergents (lysine salt of n-dodecylbenzene sulfonicacid as more specifically described in U.S. Pat. No. 3,948,818 issued onApr. 6, 1976, the specification for which is incorporated by referenceherein) with aroma nuances as set forth in Table II of Example VIII,supra are prepared containing 0.10%, 0.15% and 0.20% of the perfumesubstances as set forth in Table II of Example VIII. They are preparedby adding and homogeneously admixing the appropriate quantity offragrance formulation as set forth in Table II of Example VIII in theliquid detergents. The detergents all possess excellent aromas as setforth in Table II of Example VIII, the intensities increasing withgreater concentrations of perfume substance of Table II of Example VIII.

EXAMPLE X PREPARATION OF COLOGNES AND HANDKERCHIEF PERFUMES

Perfumery substances as set forth in Table II of Example VIII areincorporated into colognes in concentrations of 2.0%, 2.5%, 3.0%, 3.5%,4.0%, 4.5% and 5.0% in 75%, 80%, 85%, 90% and 95% aqueous food gradeethanol; and into handkerchief perfumes at concentrations of 15%, 20%,25% and 30% (in 80%, 85% and 95% aqueous food grade ethanol).Distinctive and definitive aromas as set forth in Table II of ExampleVIII are imparted to the cologne and to the handkerchief perfume at allthe levels indicated above.

EXAMPLE XI PREPARATION OF SOAP COMPOSITIONS

100 grams of soap chips (IVORY® produced by the Proctor & GambleCompany, Cincinnati, Ohio) are mixed with one gram of each of thesubstances as set forth in Table II of Example VIII, supra, untilhomogeneous compositions are obtained. In each of the cases, thehomogeneous compositions are heated under 8 atmospheres pressure at 180°C. for a period of 8 hours. The resulting liquids are placed into soapmolds. The resulting soap cakes, on cooling, manifest aromas as setforth in Table II of Example VIII.

EXAMPLE XII PREPARATION OF SOLID DETERGENT COMPOSITIONS

Detergents are prepared from the following ingredients according toExample I of Canadian Pat. No. 1,007,948, the specification for which isincorporated by reference herein:

    ______________________________________                                        Ingredients          Parts by Weight                                          ______________________________________                                             Neodol  ® 45-11 (a C.sub.14-15                                            alcohol ethoxylated with                                                                              12                                                    11 moles of ethylene oxide                                                    Sodium carbonate        55                                                    Sodium citrate          20                                                    Sodium sulfate, water   q.s.                                                  brighteners                                                              ______________________________________                                    

This detergent is a "phosphate-free" detergent. A total of 100 grams ofthis detergent per sample is admixed with 0.15 grams of each of theperfume substances of Table II of Example VIII. Each of the detergentsamples has excellent aromas as set forth in Table II of Example VIII.

EXAMPLE XIII

Utilizing the procedure of Example I at column 15 of U.S. Pat. No.3,632,396 (the specification for which is incorporated by referenceherein), a non-woven cloth substrate useful as a drier-added fabricsoftening article of manufacture is prepared wherein the substrate, thesubstrate coating and the outer coating and the perfuming material areas follows:

1. a water dissolvable paper as the substrate ("Dissolvo Paper);

2. Adogen 448 (melting point 140° F.) as the substrate coating; and

3. an outer coating having the following formulation (melting pointabout 150° F.):

57% C₂₀₋₂₂ HAPS

22% isopropyl alcohol

20% antistatic agent

1% of one of the perfumery substances as set forth in Table II ofExample VIII.

A fabric softening composition prepared as set forth above having aromacharacteristics as set forth in Table II of Example VIII consists of asubstrate having a weight of about 3 grams per 100 square inches, asubstrate coating weighing about 1.85 grams per 100 square inches ofsubstrate and an outer coating weighing about 1.4 grams per 100 squareinches of substrate is created, thereby providing a total aromatizedsubstrate and outer coating weight ratio of about 1:1 by weight of thesubstrate. The aromas as set forth in Table II of Example VIII isimparted in pleasant manners to head spaces in the dryers on operationthereof using the drier-added fabric softening non-woven fabricarticles.

What is claimed is:
 1. A process for augmenting or enhancing the aromaof a perfume composition, cologne or perfumed article comprising thestep of admixing with said perfume composition, cologne or perfumedarticle, an aroma augmenting or enhancing quantity of a product producedaccording to the process of:(a) reacting isobutyraldehyde with acetonein the presence of a catalyst selected from the group consisting of analkali metal hydroxide, an alkaline earth metal hydroxide, aluminumchloride, sulfuric acid and pyrrolidinium acetate in the presence of aninert solvent, the mole ratio of isobutyraldehyde:acetone varying fromabout 1.5:0.5 up to 0.5:1.5 isobutyraldehyde:acetone, the reactiontemperature varying from about 25° C. up to about 120° C., therebyforming a mixture of compounds defined according to the structure:##STR137## wherein in the mixture, one of the dashed lines is acarbon-carbon double bond and the other of the dashed lines is acarbon-carbon single bond; (b) then dimerizing the resulting mixture ofketones to form a mixture of cyclic dimers, the dimerization reactionbeing carried out at a temperature in the range of from about 25° C. upto about 120° C. at atmospheric pressure in the presence of ahydrocarbon solvent or an inert alkanol solvent and in the presence of acatalyst selected from the group consisting of alkali metal hydroxides,alkaline earth metal hydroxides, aluminum chloride and pyrrolidiniumacetate; and then (c) reacting the resulting ketone dimer mixture withhydrogen in the presence of a hydrogenation catalyst selected from thegroup consisting of palladium, palladium on a carbon support, palladiumon a calcium carbonate support or palladium on a barium sulfate supportat a hydrogen pressure of from 50 psig up to 10 atmospheres, the moleratio of hydrogen:ketone dimer reactant being in the range of from 1:1hydrogen:ketone dimer up to about 3:1 hydrogen:ketone dimer, thereaction being carried out in an inert solvent and the reactiontemperature varying from about 20° C. up to about 100° C.
 2. A processfor augmenting or enhancing the aroma of a perfume composition, cologneor perfumed article comprising the step of adding to said perfumecomposition, cologne or perfumed article, an aroma augmenting orenhancing quantity of a product produced according to the processcomprising the steps of:(a) reacting acetone with isobutyraldehyde inthe presence of a catalyst selected from the group consisting of alkalimetal hydroxides, alkaline earth metal hydroxides, aluminum chloride,sulfuric acid and pyrrolidinum acetate in the presence of an inertsolvent, the mole ratio of isobutyraldehyde:acetone varying from 1.5:0.5up to 0.5:1.5 isobutyraldehyde:acetone the temperature of reactionvarying from about 25° C. up to about 120° C. and the concentration ofcatalyst in the reaction mass varying from about 50 grams per liter upto about 400 grams per liter whereby a mixture of compounds is formeddefined according to the structure: ##STR138## wherein in the mixture ineach of the compounds, one of the dashed lines is a carbon-carbon doublebond and the other of the dashed lines is a carbon-carbon single bond;and then (b) dimerizing the resulting product to form a cyclic ketonedimer, said dimerization reaction being carried out at a temperature inthe range of from about 25° C. up to about 120° C. at atmosphericpressure in the presence of a hydrocarbon solvent or an inert alkanolsolvent and in the presence of a catalyst selected from the groupconsisting of alkali metal hydroxides, alkaline earth metal hydroxides,aluminum chloride and pyrrolidinium acetate; and then (c) reacting theresulting ketone dimer with an alkali metal borohydride whereby theketone moiety is reduced to a carbinol moiety in the presence of a loweralkanol solvent which is inert in the reaction mass, the concentrationof alkali metal borohydride in the reaction mass varying from about 20grams per liter of reaction mass up to about 50 grams per liter ofreaction mass, the concentration of ketone dimer in the mixture varyingfrom 200 grams per liter up to about 800 grams per liter and thereaction temperature being in the range of from 40° C. up to 70° C. 3.The process of claim 2 wherein in the process for producing the productthere exists the additional step of reacting the resultant carbinolmixture with acetic anhydride at a temperature in the range of from 90°C. up to about 120° C., the mole ratio of acetic anhydride:alcoholreactant mixture varying from about 1:0.5 up to about 2:1 alcohol:aceticanhydride.